U.S. patent application number 17/388908 was filed with the patent office on 2022-07-07 for emitting compound and organic light emitting device including the same.
This patent application is currently assigned to LG DISPLAY CO., LTD.. The applicant listed for this patent is LG DISPLAY CO., LTD.. Invention is credited to Su-Na CHOI, Jeong-Dae SEO, In-Bum SONG.
Application Number | 20220213127 17/388908 |
Document ID | / |
Family ID | |
Filed Date | 2022-07-07 |
United States Patent
Application |
20220213127 |
Kind Code |
A1 |
CHOI; Su-Na ; et
al. |
July 7, 2022 |
EMITTING COMPOUND AND ORGANIC LIGHT EMITTING DEVICE INCLUDING THE
SAME
Abstract
An emitting compound of following and an organic light emitting
device includes the flowing emitting compound. ##STR00001##
Inventors: |
CHOI; Su-Na; (Paju-si,
KR) ; SONG; In-Bum; (Paju-si, KR) ; SEO;
Jeong-Dae; (Paju-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG DISPLAY CO., LTD. |
SEOUL |
|
KR |
|
|
Assignee: |
LG DISPLAY CO., LTD.
SEOUL
KR
|
Appl. No.: |
17/388908 |
Filed: |
July 29, 2021 |
International
Class: |
C07F 5/02 20060101
C07F005/02; H01L 51/00 20060101 H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 29, 2020 |
KR |
10-2020-0186022 |
Claims
1. An emitting compound represented by Formula 1: ##STR00086##
wherein n is 0 or 1, and X is one of B, P.dbd.O and P.dbd.S,
wherein each of Y.sub.1 and Y.sub.2 is independently selected from
the group consisting of NR.sub.1, C(R.sub.2).sub.2, O, S, Se and
Si(R.sub.3).sub.2, and Y.sub.3 is O or S, wherein each of Z.sub.1
to Z.sub.4 is independently N or CR.sub.4, and at least three of
Z.sub.1 to Z.sub.4 are CR.sub.4, wherein each of R.sub.1 to R.sub.3
is independently selected from the group consisting of hydrogen,
deuterium, C1 to C10 alkyl group unsubstituted or substituted with
deuterium, C6 to C30 arylamine group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, wherein each of R.sub.4 to R.sub.6 is
independently selected from the group consisting of hydrogen,
deuterium, C1 to C10 alkyl group unsubstituted or substituted with
deuterium, C6 to C30 arylamine group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, or adjacent two of R.sub.4 to R.sub.6
are connected to each other to form a fused ring, and at least one
of R.sub.4 to R.sub.6 is C1 to C10 alkyl substituted with
deuterium, and wherein each of A and B rings is independently
selected from the group consisting of substituted or unsubstituted
six-membered cycloalkyl ring, substituted or unsubstituted
six-membered aromatic ring and substituted or unsubstituted
six-membered heteroaromatic ring.
2. The emitting compound according to claim 1, wherein the Formula
1 is represented by Formula 2-1: ##STR00087##
3. The emitting compound according to claim 2, wherein the Formula
2-1 is represented by Formula 2-2: ##STR00088## wherein in the
Formula 2-2, one of Z.sub.1 to Z.sub.4 is N, and three of Z.sub.1
to Z.sub.4 are CR.sub.4, wherein at least one of three R.sub.4 is
deuterium-substituted C1 to C10 alkyl group, and wherein each of
R.sub.11 to R.sub.17 is independently selected from the group
consisting of hydrogen, deuterium, C1 to C10 alkyl group
unsubstituted or substituted with deuterium, C6 to C30 arylamine
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, C6 to C30 aryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl.
4. The emitting compound according to claim 1, wherein the Formula
1 is represented by Formula 3-1: ##STR00089##
5. The emitting compound according to claim 4, wherein the Formula
3-1 is represented by Formula 3-2: ##STR00090## wherein in the
Formula 3-2, adjacent two of R.sub.4 are connected to each other to
form a fused ring, and at least one of the other two R.sub.4 is
deuterium-substituted C1 to C10 alkyl, and wherein each of R.sub.21
to R.sub.27 is independently selected from the group consisting of
hydrogen, deuterium, C1 to C10 alkyl group unsubstituted or
substituted with deuterium, C6 to C30 arylamine group unsubstituted
or substituted with deuterium or C1 to C10 alkyl, C6 to C30 aryl
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, and C5 to C30 heteroaryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl.
6. The emitting compound according to claim 1, wherein the Formula
1 is represented by Formula 4-1: ##STR00091##
7. The emitting compound according to claim 6, wherein the Formula
4-1 is represented by one of Formulas 4-2 to 4-4: ##STR00092##
wherein in the Formulas 4-2 to 4-4, one of Z.sub.1 to Z.sub.4 is N,
and three of Z.sub.1 to Z.sub.4 are CR.sub.4, wherein at least one
of three R.sub.4 is deuterium-substituted C1 to C10 alkyl group,
and wherein each of R.sub.31 to R.sub.37 is independently selected
from the group consisting of hydrogen, deuterium, C1 to C10 alkyl
group unsubstituted or substituted with deuterium, C6 to C30
arylamine group unsubstituted or substituted with deuterium or C1
to C10 alkyl, C6 to C30 aryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl.
8. The emitting compound according to claim 7, wherein the Formulas
4-2 to 4-4 are respectively represented by Formulas 4-5 to 4-7:
##STR00093## wherein in the Formulas 4-5 to 4-7, Y.sub.4 is O or S,
wherein one of Z.sub.5 to Z.sub.8 is N, and the other three of
Z.sub.5 to Z.sub.8 are CR.sub.7, wherein each of three R.sub.7 is
independently selected from the group consisting of hydrogen,
deuterium, C1 to C10 alkyl group unsubstituted or substituted with
deuterium, C6 to C30 arylamine group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, and at least one of three R.sub.7 is
deuterium-substituted C1 to C10 alkyl group, and wherein each of
R.sub.35 to R.sub.37 is independently selected from the group
consisting of hydrogen, deuterium, C1 to C10 alkyl group
unsubstituted or substituted with deuterium, C6 to C30 arylamine
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, C6 to C30 aryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl.
9. The emitting compound according to claim 1, wherein the Formula
1 is represented by Formula 5-1: ##STR00094##
10. The emitting compound according to claim 9, wherein the Formula
5-1 is represented by Formula 5-2: ##STR00095## wherein in the
Formula 5-2, adjacent two of four R.sub.4 or R.sub.5 and R.sub.6 is
connected to form a fused ring, and at least one of the other four
of R.sub.4, R.sub.5 and R.sub.6 is deuterium-substituted C1 to C10
alkyl group, and wherein each of R.sub.41 to R.sub.47 is
independently selected from the group consisting of hydrogen,
deuterium, C1 to C10 alkyl group unsubstituted or substituted with
deuterium, C6 to C30 arylamine group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl.
11. The emitting compound according to claim 9, wherein the Formula
5-1 is represented by Formula 5-3: ##STR00096## wherein in the
Formula 5-3, Y.sub.5 is O or S, wherein adjacent two of four
R.sub.4 or R.sub.5 and R.sub.6 is connected to form a fused ring,
and at least one of the other four of R.sub.4, R.sub.5 and R.sub.6
is deuterium-substituted C1 to C10 alkyl group, wherein each of
R.sub.8, R.sub.9 and R.sub.51 to R.sub.54 is independently selected
from the group consisting of hydrogen, deuterium, C1 to C10 alkyl
group unsubstituted or substituted with deuterium, C6 to C30
arylamine group unsubstituted or substituted with deuterium or C1
to C10 alkyl, C6 to C30 aryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, or
adjacent two of R.sub.51 to R.sub.54 or R.sub.8 and R.sub.9 is
connected to form a fused ring, wherein at least one of the other
four of R.sub.8, R.sub.9 and R.sub.51 to R.sub.54 is
deuterium-substituted C1 to C10 alkyl group, and wherein each of
R.sub.55 to R.sub.54 is independently selected from the group
consisting of hydrogen, deuterium, C1 to C10 alkyl group
unsubstituted or substituted with deuterium, C6 to C30 arylamine
group unsubstituted or substituted with deuterium or C to C10
alkyl, C6 to C30 aryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl.
12. The emitting compound according to claim 11, wherein the
Formula 5-3 is represented by Formula 5-4: ##STR00097##
13. The emitting compound according to claim 1, wherein the
emitting compound is one compounds in Formula 6: ##STR00098##
##STR00099## ##STR00100## ##STR00101## ##STR00102##
##STR00103##
14. An organic light emitting device, comprising: a substrate; and
an organic light emitting diode positioned on the substrate and
including a first electrode; a second electrode facing the first
electrode; and a first emitting material layer including a first
compound and positioned between the first and second electrodes,
wherein the first compound is the emitting compound of claim 1.
15. The organic light emitting device of claim 14, wherein the
first emitting material layer further includes a second compound,
wherein the second compound is represented by Formula 7:
##STR00104## wherein each of Ar.sub.1 and Ar.sub.2 is independently
C6 to C30 aryl group or C5 to C30 heteroaryl group, L is a single
bond or C6 to C30 arylene group, and wherein hydrogens are not
deuterated or partially or wholly deuterated.
16. The organic light emitting device of claim 14, wherein the
organic light emitting diode further includes: a second emitting
material layer including a third compound and positioned between
the first emitting material layer and the second electrode; and a
first charge generation layer between the first and second emitting
material layers, and wherein the third compound is the emitting
compound of claim 1.
17. The organic light emitting device of claim 16, wherein the
organic light emitting diode further includes: a third emitting
material layer positioned between the first charge generation layer
and the second emitting material layer; and a second charge
generation layer between the second and third emitting material
layers, and wherein the third emitting material layer emits a
yellow-green light or red and green lights.
18. The organic light emitting device of claim 14, wherein the
organic light emitting diode further includes: a second emitting
material layer emitting a yellow-green light and positioned between
the first emitting material layer and the second electrode; and a
charge generation layer between the first and second emitting
material layers.
19. The organic light emitting device of claim 14, wherein a red
pixel, a green pixel and a blue pixel are defined on the substrate,
and the organic light emitting diode corresponds to each of the
red, green and blue pixels, and wherein the organic light emitting
device further includes a color filter layer disposed between the
substrate and the organic light emitting diode or on the organic
light emitting diode and corresponding to the red, green and blue
pixels.
20. The organic light emitting device of claim 14, wherein the
first compound is one compounds in Formula 8: ##STR00105##
##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110##
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of Korean Patent
Application No. 10-2020-0186022 filed on Dec. 29, 2020, which is
hereby incorporated by reference in its entirety.
BACKGROUND
Field of the Disclosure
[0002] The present disclosure relates to an emitting compound, and
more specifically, to an emitting compound having high emitting
efficiency and lifespan and an organic light emitting device
including the same.
Description of the Background
[0003] As requests for a flat panel display device having a small
occupied area have been increased, an organic light emitting
display device including an organic light emitting diode (OLED) has
been the subject of recent research and development.
[0004] The OLED emits light by injecting electrons from a cathode
as an electron injection electrode and holes from an anode as a
hole injection electrode into an emitting material layer (EML),
combining the electrons with the holes, generating an exciton, and
transforming the exciton from an excited state to a ground state. A
flexible substrate, for example, a plastic substrate, can be used
as a base substrate where elements are formed. In addition, the
organic light emitting display device can be operated at a voltage
(e.g., 10V or below) lower than a voltage required to operate other
display devices. Moreover, the organic light emitting display
device has advantages in the power consumption and the color
sense.
[0005] For example, the organic light emitting display device may
include a red pixel region, a green pixel region and a blue pixel
region, and the OLED may be formed in each of the red, green and
blue pixel regions.
[0006] However, the OLED in the blue pixel does not provide
sufficient emitting efficiency and lifespan such that the organic
light emitting display device has a limitation in the emitting
efficiency and the lifespan.
SUMMARY
[0007] The present disclosure is directed to an emitting compound
and an organic light emitting device including the emitting
compound that substantially obviate one or more of the problems
associated with the limitations and disadvantages of the related
conventional art.
[0008] Additional features and advantages of the present disclosure
are set forth in the description which follows, and will be
apparent from the description, or evident by practice of the
present disclosure. The features and other advantages of the
present disclosure are realized and attained by the features
described herein as well as in the appended drawings.
[0009] To achieve these and other advantages in accordance with the
purpose of the aspects of the present disclosure, as described
herein, an aspect of the present disclosure is an emitting compound
represented by Formula 1:
##STR00002##
[0010] wherein n is 0 or 1, and X is one of B, P.dbd.O and P.dbd.S,
wherein each of Y.sub.1 and Y.sub.2 is independently selected from
the group consisting of NR.sub.1, C(R.sub.2).sub.2, O, S, Se and
Si(R.sub.3).sub.2, and Y.sub.3 is O or S, wherein each of Z.sub.1
to Z.sub.4 is independently N or CR.sub.4, and at least three of
Z.sub.1 to Z.sub.4 are CR.sub.4, wherein each of R.sub.1 to R.sub.3
is independently selected from the group consisting of hydrogen,
deuterium, C1 to C10 alkyl group unsubstituted or substituted with
deuterium, C6 to C30 arylamine group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, wherein each of R.sub.4 to R.sub.6 is
independently selected from the group consisting of hydrogen,
deuterium, C1 to C10 alkyl group unsubstituted or substituted with
deuterium, C6 to C30 arylamine group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, or adjacent two of R.sub.4 to R.sub.6
are connected to each other to form a fused ring, and at least one
of R.sub.4 to R.sub.6 is C1 to C10 alkyl substituted with
deuterium, and wherein each of A and B rings is independently
selected from the group consisting of substituted or unsubstituted
six-membered cycloalkyl ring, substituted or unsubstituted
six-membered aromatic ring and substituted or unsubstituted
six-membered heteroaromatic ring.
[0011] Another aspect of the present disclosure is an organic light
emitting device comprising a substrate; and an organic light
emitting diode positioned on the substrate and including a first
electrode; a second electrode facing the first electrode; and a
first emitting material layer including a first compound and
positioned between the first and second electrodes, wherein the
first compound is the above emitting compound.
[0012] It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory and are intended to further explain the present
disclosure as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The accompanying drawings, which are included to provide a
further understanding of the present disclosure and are
incorporated in and constitute a part of this specification,
illustrate aspects of the present disclosure and together with the
description serve to explain the principles of the present
disclosure.
[0014] FIG. 1 is a schematic circuit diagram illustrating an
organic light emitting display device of the present
disclosure;
[0015] FIG. 2 is a schematic cross-sectional view illustrating an
organic light emitting display device according to a first aspect
of the present disclosure;
[0016] FIG. 3 is a schematic cross-sectional view illustrating an
OLED having a single emitting part for the organic light emitting
display device according to the first aspect of the present
disclosure;
[0017] FIG. 4 is a schematic cross-sectional view illustrating an
OLED having a tandem structure of two emitting parts for the
organic light emitting display device according to the first aspect
of the present disclosure;
[0018] FIG. 5 is a schematic cross-sectional view illustrating an
organic light emitting display device according to a second aspect
of the present disclosure;
[0019] FIG. 6 is a schematic cross-sectional view illustrating an
OLED having a tandem structure of two emitting parts for the
organic light emitting display device according to the second
aspect of the present disclosure;
[0020] FIG. 7 is a schematic cross-sectional view illustrating an
OLED having a tandem structure of three emitting parts for the
organic light emitting display device according to the second
aspect of the present disclosure; and
[0021] FIG. 8 is a schematic cross-sectional view illustrating an
organic light emitting display device according to a third aspect
of the present disclosure.
DETAILED DESCRIPTION
[0022] Reference will now be made in detail to some of the examples
and aspects, which are illustrated in the accompanying
drawings.
[0023] FIG. 1 is a schematic circuit diagram illustrating an
organic light emitting display device of the present
disclosure.
[0024] As illustrated in FIG. 1, a gate line GL and a data line DL,
which cross each other to define a pixel (pixel region) P, and a
power line PL are formed in an organic light emitting display
device. A switching thin film transistor (TFT) Ts, a driving TFT
Td, a storage capacitor Cst and an OLED D are formed in the pixel
region P. The pixel region P may include a red pixel, a green pixel
and a blue pixel.
[0025] The switching thin film transistor Ts is connected to the
gate line GL and the data line DL, and the driving thin film
transistor Td and the storage capacitor Cst are connected between
the switching thin film transistor Ts and the power line PL. The
OLED D is connected to the driving thin film transistor Td. When
the switching thin film transistor Ts is turned on by the gate
signal applied through the gate line GL, the data signal applied
through the data line DL is applied a gate electrode of the driving
thin film transistor Td and one electrode of the storage capacitor
Cst through the switching thin film transistor Ts.
[0026] The driving thin film transistor Td is turned on by the data
signal applied into the gate electrode so that a current
proportional to the data signal is supplied from the power line PL
to the OLED D through the driving thin film transistor Td. The OLED
D emits light having a luminance proportional to the current
flowing through the driving thin film transistor Td. In this case,
the storage capacitor Cst is charge with a voltage proportional to
the data signal so that the voltage of the gate electrode in the
driving thin film transistor Td is kept constant during one frame.
Therefore, the organic light emitting display device can display a
desired image.
[0027] FIG. 2 is a schematic cross-sectional view illustrating an
organic light emitting display device according to a first aspect
of the present disclosure.
[0028] As illustrated in FIG. 2, the organic light emitting display
device 100 includes a substrate 110, a TFT Tr and an OLED D
connected to the TFT Tr. For example, the organic light emitting
display device 100 may include a red pixel, a green pixel and a
blue pixel, and the OLED D may be formed in each of the red, green
and blue pixels. Namely, the OLEDs D emitting red light, green
light and blue light may be provided in the red, green and blue
pixels, respectively.
[0029] The substrate 110 may be a glass substrate or a flexible
substrate. For example, the flexible substrate may be a polyimide
(PI) substrate, a polyethersulfone (PES) substrate, a
polyethylenenaphthalate (PEN) substrate, a polyethylene
terephthalate (PET) substrate or a polycarbonate (PC)
substrate.
[0030] A buffer layer 120 is formed on the substrate, and the TFT
Tr is formed on the buffer layer 120. The buffer layer 120 may be
omitted.
[0031] A semiconductor layer 122 is formed on the buffer layer 120.
The semiconductor layer 122 may include an oxide semiconductor
material or polycrystalline silicon.
[0032] When the semiconductor layer 122 includes the oxide
semiconductor material, a light-shielding pattern (not shown) may
be formed under the semiconductor layer 122. The light to the
semiconductor layer 122 is shielded or blocked by the
light-shielding pattern such that thermal degradation of the
semiconductor layer 122 can be prevented. On the other hand, when
the semiconductor layer 122 includes polycrystalline silicon,
impurities may be doped into both sides of the semiconductor layer
122.
[0033] A gate insulating layer 124 is formed on the semiconductor
layer 122. The gate insulating layer 124 may be formed of an
inorganic insulating material such as silicon oxide or silicon
nitride.
[0034] A gate electrode 130, which is formed of a conductive
material, e.g., metal, is formed on the gate insulating layer 124
to correspond to a center of the semiconductor layer 122.
[0035] In FIG. 2, the gate insulating layer 124 is formed on an
entire surface of the substrate 110. Alternatively, the gate
insulating layer 124 may be patterned to have the same shape as the
gate electrode 130.
[0036] An interlayer insulating layer 132, which is formed of an
insulating material, is formed on the gate electrode 130. The
interlayer insulating layer 132 may be formed of an inorganic
insulating material, e.g., silicon oxide or silicon nitride, or an
organic insulating material, e.g., benzocyclobutene or
photo-acryl.
[0037] The interlayer insulating layer 132 includes first and
second contact holes 134 and 136 exposing both sides of the
semiconductor layer 122. The first and second contact holes 134 and
136 are positioned at both sides of the gate electrode 130 to be
spaced apart from the gate electrode 130.
[0038] The first and second contact holes 134 and 136 are formed
through the gate insulating layer 124. Alternatively, when the gate
insulating layer 124 is patterned to have the same shape as the
gate electrode 130, the first and second contact holes 134 and 136
is formed only through the interlayer insulating layer 132.
[0039] A source electrode 140 and a drain electrode 142, which are
formed of a conductive material, e.g., metal, are formed on the
interlayer insulating layer 132.
[0040] The source electrode 140 and the drain electrode 142 are
spaced apart from each other with respect to the gate electrode 130
and respectively contact both sides of the semiconductor layer 122
through the first and second contact holes 134 and 136.
[0041] The semiconductor layer 122, the gate electrode 130, the
source electrode 140 and the drain electrode 142 constitute the TFT
Tr. The TFT Tr serves as a driving element. Namely, the TFT Tr may
correspond to the driving TFT Td (of FIG. 1).
[0042] In the TFT Tr, the gate electrode 130, the source electrode
140, and the drain electrode 142 are positioned over the
semiconductor layer 122. Namely, the TFT Tr has a coplanar
structure.
[0043] Alternatively, in the TFT Tr, the gate electrode may be
positioned under the semiconductor layer, and the source and drain
electrodes may be positioned over the semiconductor layer such that
the TFT Tr may have an inverted staggered structure. In this
instance, the semiconductor layer may include amorphous
silicon.
[0044] Although not shown, the gate line and the data line cross
each other to define the pixel, and the switching TFT is formed to
be connected to the gate and data lines. The switching TFT is
connected to the TFT Tr as the driving element.
[0045] In addition, the power line, which may be formed to be
parallel to and spaced apart from one of the gate and data lines,
and the storage capacitor for maintaining the voltage of the gate
electrode of the TFT Tr in one frame may be further formed.
[0046] A passivation layer 150, which includes a drain contact hole
152 exposing the drain electrode 142 of the TFT Tr, is formed to
cover the TFT Tr.
[0047] A first electrode 160, which is connected to the drain
electrode 142 of the TFT Tr through the drain contact hole 152, is
separately formed in each pixel and on the passivation layer 150.
The first electrode 160 may be an anode and may be formed of a
conductive material, e.g., a transparent conductive oxide (TCO),
having a relatively high work function. For example, the first
electrode 160 may be formed of indium-tin-oxide (ITO),
indium-zinc-oxide (IZO), indium-tin-zinc-oxide (ITZO), tin oxide
(SnO), zinc oxide (ZnO), indium-copper-oxide (ICO) or
aluminum-zinc-oxide (Al:ZnO, AZO).
[0048] When the organic light emitting display device 100 is
operated in a bottom-emission type, the first electrode 160 may
have a single-layered structure of the transparent conductive
material layer. When the Organic light emitting display device 100
is operated in a top-emission type, a reflection electrode or a
reflection layer may be formed under the first electrode 160. For
example, the reflection electrode or the reflection layer may be
formed of silver (Ag) or aluminum-palladium-copper (APC) alloy. In
this instance, the first electrode 160 may have a triple-layered
structure of ITO/Ag/ITO or ITO/APC/ITO.
[0049] A bank layer 166 is formed on the passivation layer 150 to
cover an edge of the first electrode 160. Namely, the bank layer
166 is positioned at a boundary of the pixel and exposes a center
of the first electrode 160 in the pixel.
[0050] An organic emitting layer 162 is formed on the first
electrode 160. The organic emitting layer 162 may have a
single-layered structure of an emitting material layer including an
emitting material. To increase an emitting efficiency of the OLED D
and/or the organic light emitting display device 100, the organic
emitting layer 162 may have a multi-layered structure.
[0051] The organic emitting layer 162 is separated in each of the
red, green and blue pixels. As illustrated below, the organic
emitting layer 162 in the blue pixel includes an emitting compound
of Formula 1 such that the emitting efficiency and the lifespan of
the OLED D in the blue pixel are improved.
[0052] A second electrode 164 is formed over the substrate 110
where the organic emitting layer 162 is formed. The second
electrode 164 covers an entire surface of the display area and may
be formed of a conductive material having a relatively low work
function to serve as a cathode. For example, the second electrode
164 may be formed of aluminum (Al), magnesium (Mg), calcium (Ca),
silver (Ag) or their alloy or combination. In the top-emission type
organic light emitting display device 100, the second electrode 164
may have a thin profile (small thickness) to provide a light
transmittance property (or a semi-transmittance property).
[0053] The first electrode 160, the organic emitting layer 162 and
the second electrode 164 constitute the OLED D.
[0054] An encapsulation film 170 is formed on the second electrode
164 to prevent penetration of moisture into the OLED D. The
encapsulation film 170 includes a first inorganic insulating layer
172, an organic insulating layer 174 and a second inorganic
insulating layer 176 sequentially stacked, but it is not limited
thereto. The encapsulation film 170 may be omitted.
[0055] The Organic light emitting display device 100 may further
include a polarization plate (not shown) for reducing an ambient
light reflection. For example, the polarization plate may be a
circular polarization plate. In the bottom-emission type organic
light emitting display device 100, the polarization plate may be
disposed under the substrate 110. In the top-emission type organic
light emitting display device 100, the polarization plate may be
disposed on or over the encapsulation film 170.
[0056] In addition, in the top-emission type organic light emitting
display device 100, a cover window (not shown) may be attached to
the encapsulation film 170 or the polarization plate. In this
instance, the substrate 110 and the cover window have a flexible
property such that a flexible organic light emitting display device
may be provided.
[0057] FIG. 3 is a schematic cross-sectional view illustrating an
OLED having a single emitting unit for the organic light emitting
display device according to the first aspect of the present
disclosure.
[0058] As illustrated in FIG. 3, the OLED D includes the first and
second electrodes 160 and 164, which face each other, and the
organic emitting layer 162 therebetween. The organic emitting layer
162 includes an emitting material layer (EML) 240 between the first
and second electrodes 160 and 164. The organic light emitting
display device 100 (of FIG. 2) may include a red pixel, a green
pixel and a blue pixel, and the OLED D may be positioned in the
blue pixel.
[0059] One of the first and second electrodes 160 and 164 is an
anode, and the other one of the first and second electrodes 160 and
164 is cathode. In addition, one of the first and second electrodes
160 and 164 may be a transparent (or a semi-transparent) electrode,
and the other one of the first and second electrodes 160 and 164
may be a reflection electrode.
[0060] The organic emitting layer 162 may further include an
electron blocking layer (EBL) 230 between the first electrode 160
and the EML 240 and a hole blocking layer (HBL) 250 between the EML
240 and the second electrode 164.
[0061] In addition, the organic emitting layer 162 may further
include a hole transporting layer (HTL) 220 between the first
electrode 160 and the EBL 230.
[0062] Moreover, the organic emitting layer 162 may further include
a hole injection layer (HIL) 210 between the first electrode 160
and the HTL 220 and an electron injection layer (EIL) 260 between
the second electrode 164 and the HBL 250.
[0063] The EML 240 includes an emitting compound 242 as a first
compound. The emitting compound is a polycyclic aromatic compound
and is represented by Formula 1.
##STR00003##
[0064] In Formula 1, n is 0 or 1, and X is one of B, P.dbd.O and
P.dbd.S. Each of Y.sub.1 and Y.sub.2 is independently selected from
the group consisting of NR.sub.1, C(R.sub.2).sub.2, O, S, Se and
Si(R.sub.3).sub.2, and Y.sub.3 is O or S. Each of Z.sub.1 to
Z.sub.4 is independently N or CR.sub.4, and at least three of
Z.sub.1 to Z.sub.4 are CR.sub.4. Each of R.sub.1 to R.sub.3 is
independently selected from the group consisting of hydrogen,
deuterium (D), C1 to C10 alkyl group unsubstituted or substituted
with deuterium, C6 to C30 arylamine group unsubstituted or
substituted with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl. In addition, each of R.sub.4 to
R.sub.6 is independently selected from the group consisting of
hydrogen, deuterium, C1 to C10 alkyl group unsubstituted or
substituted with deuterium, C6 to C30 arylamine group unsubstituted
or substituted with deuterium or C1 to C10 alkyl, C6 to C30 aryl
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, and C5 to C30 heteroaryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, or adjacent two of R.sub.4 to
R.sub.6 are connected (combined) to each other to form a fused
ring. At least one of R.sub.4 to R.sub.6 is C1 to C10 alkyl
substituted with deuterium.
[0065] Each of A and B rings is independently selected from the
group consisting of substituted or unsubstituted six-membered
cycloalkyl ring, substituted or unsubstituted six-membered aromatic
ring and substituted or unsubstituted six-membered heteroaromatic
ring.
[0066] The fused ring may be C6 to C30 aromatic ring or C5 to C30
heteroaromatic (fused) ring. For example, the fused ring of C6 to
C30 aromatic ring may be benzene ring or naphthalene ring.
[0067] In each of the A and B rings, hydrogen may be substituted by
at least one of D, C1 to C10 alkyl group unsubstituted or
substituted with deuterium, C6 to C30 aryl group and C5 to C30
heteroaryl group.
[0068] For example, in Formula 1, n may be 0. Namely, the
five-membered ring including Y.sub.3 may be directly connected to X
and Y.sub.2, and the emitting compound in Formula 1 may be
represented by Formula 2-1.
##STR00004##
[0069] In addition, in Formula 2-1, X may be B, each of Y.sub.1 and
Y.sub.2 may be NR.sub.1, and each of the A and B rings may be a
benzene ring. Namely, the emitting compound in Formula 1 may be
represented by Formula 2-2.
##STR00005##
[0070] In Formula 2-2, one of Z.sub.1 to Z.sub.4 is N, and three of
Z.sub.1 to Z.sub.4 are CR.sub.4. At least one of three R.sub.4 is
D-substituted C1 to C10 alkyl group. Each of R.sub.11 to R.sub.17
is independently selected from the group consisting of hydrogen,
deuterium (D), C1 to C10 alkyl group unsubstituted or substituted
with deuterium, C6 to C30 arylamine group unsubstituted or
substituted with deuterium or C1 to C10 alkyl, C6 to C30 aryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
C5 to C30 heteroaryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl.
[0071] For example, in Formula 2-2, R.sub.1 may be C6 to C30 aryl,
e.g., phenyl. One of three R.sub.4 may be D-substituted C1 to C10
alkyl, e.g., CD3, and the other two of three R.sub.4 may be
hydrogen. In addition, R.sub.11 to R.sub.17 may be hydrogen. The
compound of Formula 2-1 or Formula 2-2 may be one of the compounds
1-1 to 1-10 in Formula 6.
[0072] Alternatively, in Formula 1, n may be O, and Z.sub.1 to
Z.sub.4 may be CR.sub.4. Namely, the emitting compound in Formula 1
may be represented by Formula 3-1.
##STR00006##
[0073] In addition, in Formula 3-1, X may be B, each of Y.sub.1 and
Y.sub.2 may be NR.sub.1, and each of the A and B rings may be a
benzene ring. Namely, the emitting compound in Formula 1 may be
represented by Formula 3-2.
##STR00007##
[0074] In Formula 3-2, adjacent two of R.sub.4 are connected to
each other to form a fused ring, and at least one of the other two
R.sub.4 is D-substituted C1 to C10 alkyl. In addition, each of
R.sub.21 to R.sub.27 is independently selected from the group
consisting of hydrogen, D, C1 to C10 alkyl group unsubstituted or
substituted with deuterium, C6 to C30 arylamine group unsubstituted
or substituted with deuterium or C1 to C10 alkyl, C6 to C30 aryl
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, and C5 to C30 heteroaryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl.
[0075] For example, in Formula 3-2, R.sub.1 may be C6 to C30 aryl,
e.g., phenyl. One of the other two R.sub.4 may be CD.sub.3, and the
other one of the other two R.sub.4 may be hydrogen. In addition,
the fused ring formed by adjacent two of R.sub.4 may be C6 to C30
aromatic ring, e.g., benzene ring, and R.sub.21 to R.sub.27 may be
hydrogen. The compound of Formula 3-1 or Formula 3-2 may be one of
the compounds 2-1 to 2-6 in Formula 6.
[0076] Alternatively, in Formula 1, n may be 1. Namely, the
emitting compound in Formula 1 may be represented by Formula
4-1.
##STR00008##
[0077] In addition, in Formula 4-1, X may be B, each of Y.sub.1 and
Y.sub.2 may be NR.sub.1, and each of the A and B rings may be a
benzene ring. In this instance, depending on a combing position of
the five-membered ring including Y.sub.3, the emitting compound in
Formula 4-1 may be represented by one of Formulas 4-2 to 4-4.
##STR00009##
[0078] In Formulas 4-2 to 4-4, one of Z.sub.1 to Z.sub.4 is N, and
three of Z.sub.1 to Z.sub.4 are CR.sub.4. At least one of three
R.sub.4 is D-substituted C1 to C10 alkyl group. Each of R.sub.31 to
R.sub.37 is independently selected from the group consisting of
hydrogen, deuterium (D), C1 to C10 alkyl group unsubstituted or
substituted with deuterium, C6 to C30 arylamine group unsubstituted
or substituted with deuterium or C1 to C10 alkyl, C6 to C30 aryl
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, and C5 to C30 heteroaryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl.
[0079] For example, in Formulas 4-2 to 4-4, R.sub.1 may be C6 to
C30 aryl, e.g., phenyl. One of three R.sub.4 may be D-substituted
C1 to C10 alkyl, e.g., CD3, and the other two of three R.sub.4 may
be hydrogen. In addition, R.sub.31 to R.sub.37 may be hydrogen. The
compound of Formulas 4-1 to Formula 4-4 may be one of the compounds
3-1 to 3-9 in Formula 6.
[0080] Alternatively, in each of Formulas 4-2 to 4-4, adjacent two
of R.sub.31 to R.sub.34 may be connected to each other to form a
hetero-fused ring. Namely, the emitting compound of the present
disclosure may be represented by one of Formulas 4-5 to 4-7.
##STR00010##
[0081] In each of Formulas 4-5 to 4-7, Y.sub.4 is O or S. One of
Z.sub.5 to Z.sub.8 is N, and the other three of Z.sub.5 to Z.sub.8
are CR.sub.7. Each of three R.sub.7 is independently selected from
the group consisting of hydrogen, deuterium, C1 to C10 alkyl group
unsubstituted or substituted with deuterium, C6 to C30 arylamine
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, C6 to C30 aryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, and
at least one of three R.sub.7 is D-substituted C1 to C10 alkyl
group.
[0082] Each of R.sub.35 to R.sub.37 is independently selected from
the group consisting of hydrogen, deuterium (D), C1 to C10 alkyl
group unsubstituted or substituted with deuterium, C6 to C30
arylamine group unsubstituted or substituted with deuterium or C1
to C10 alkyl, C6 to C30 aryl group unsubstituted or substituted
with deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl.
[0083] For example, in each of Formulas 4-5 to 4-7, R.sub.1 may be
C6 to C30 aryl, e.g., phenyl. One of three R.sub.7 may be
D-substituted C1 to C10 alkyl, e.g., CD3, and the other two of
three R.sub.7 may be hydrogen. In addition, R.sub.35 to R.sub.37
may be hydrogen.
[0084] Alternatively, in Formula 1, n may be 1, and Z.sub.1 to
Z.sub.4 are CR.sub.4. Namely, the emitting compound in Formula 1
may be represented by Formula 5-1.
##STR00011##
[0085] In addition, in Formula 5-1, X may be B, each of Y.sub.1 and
Y.sub.2 may be NR.sub.1, and each of the A and B rings may be a
benzene ring. Namely, the emitting compound in Formula 1 may be
represented by one of Formula 5-2.
##STR00012##
[0086] In Formula 5-2, adjacent two of four R.sub.4 or R.sub.5 and
R.sub.6 is connected to form a fused ring, and at least one of the
other four of R.sub.4, R.sub.5 and R.sub.6 is D-substituted C1 to
C10 alkyl group. Each of R.sub.41 to R.sub.47 is independently
selected from the group consisting of hydrogen, deuterium (D), C1
to C10 alkyl group unsubstituted or substituted with deuterium, C6
to C30 arylamine group unsubstituted or substituted with deuterium
or C1 to C10 alkyl, C6 to C30 aryl group unsubstituted or
substituted with deuterium or C1 to C10 alkyl, and C5 to C30
heteroaryl group unsubstituted or substituted with deuterium or C1
to C10 alkyl.
[0087] For example, in Formula 5-2, R.sub.1 may be C6 to C30 aryl,
e.g., phenyl. One of the other four of R.sub.4, R.sub.5 and R.sub.6
may be D-substituted C1 to C10 alkyl, e.g., CD3, and the other of
the other four of R.sub.4, R.sub.5 and R.sub.6 may be hydrogen. The
fused ring formed by adjacent two of four R.sub.4 or R.sub.5 and
R.sub.6 may be C6 to C30 aromatic ring, e.g., benzene ring, and
R.sub.41 to R.sub.47 may be hydrogen. The compound of Formula 5-1
or Formula 5-2 may be one of the compounds 4-1 to 4-4 in Formula
6.
[0088] Alternatively, in Formula 5-1, the A ring may be benzene
ring, and the B ring may be heteroaromatic fused ring. Namely, the
emitting compound in Formula 5-1 may be represented by Formula
5-3.
##STR00013##
[0089] In Formula 5-3, Y.sub.5 is O or S. Adjacent two of four
R.sub.4 or R.sub.5 and R.sub.6 is connected to form a fused ring,
and at least one of the other four of R.sub.4, R.sub.5 and R.sub.6
is D-substituted C1 to C10 alkyl group. Each of R.sub.8, R.sub.9
and R.sub.51 to R.sub.54 is independently selected from the group
consisting of hydrogen, deuterium (D), C1 to C10 alkyl group
unsubstituted or substituted with deuterium, C6 to C30 arylamine
group unsubstituted or substituted with deuterium or C1 to C10
alkyl, C6 to C30 aryl group unsubstituted or substituted with
deuterium or C1 to C10 alkyl, and C5 to C30 heteroaryl group
unsubstituted or substituted with deuterium or C1 to C10 alkyl, or
adjacent two of R.sub.51 to R.sub.54 or R.sub.8 and R.sub.9 is
connected to form a fused ring. At least one of the other four of
R.sub.8, R.sub.9 and R.sub.51 to R.sub.54 is D-substituted C1 to
C10 alkyl group. Each of R.sub.55 to R.sub.57 is independently
selected from the group consisting of hydrogen, deuterium (D), C1
to C10 alkyl group unsubstituted or substituted with deuterium, C6
to C30 arylamine group unsubstituted or substituted with deuterium
or C1 to C10 alkyl, C6 to C30 aryl group unsubstituted or
substituted with deuterium or C1 to C10 alkyl, and C5 to C30
heteroaryl group unsubstituted or substituted with deuterium or C1
to C10 alkyl.
[0090] In Formula 5-3, X may be B, each of Y.sub.1 and Y.sub.2 may
be NR.sub.1. Namely, the emitting compound in Formula 5-3 may be
represented by Formula 5-4.
##STR00014##
[0091] For example, in Formula 5-4, R.sub.1 may be C6 to C30 aryl,
e.g., phenyl. One of the other four of R.sub.4, R.sub.5 and R.sub.6
may be D-substituted C1 to C10 alkyl, e.g., CD3, and the other of
the other four of R.sub.4, R.sub.5 and R.sub.6 may be hydrogen.
Each of the fused ring formed by adjacent two of four R.sub.4 or
R.sub.5 and R.sub.6 and the fused ring formed by adjacent two of
R.sub.51 to R.sub.54 or R.sub.8 and R.sub.9 may be C6 to C30
aromatic ring, e.g., benzene ring, and R.sub.55 to R.sub.57 may be
hydrogen. The compound of Formula 5-3 or Formula 5-4 may be one of
the compounds 4-5 to 4-8 in Formula 6.
[0092] The emitting compound of the present disclosure may be one
of compounds in Formula 6.
##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##
##STR00020## ##STR00021## ##STR00022##
[0093] The emitting compound in Formulas 1 to 6 provides blue
emission and is used for the EML 240 in the OLED D. As a result,
the lifespan of the OLED D and the organic light emitting device
100 is significantly increased.
[0094] Synthesis of the Host
[0095] 1. Synthesis of Compound 1-1
[0096] (1) Compound I1-1c
##STR00023##
[0097] In the 500 mL reactor, the compound I1-1a 8.5 g (50 mmol),
the compound I1-1b 18.6 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred/refluxed for 5 hours. After completion of the
reaction, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 17.2 g of the
compound I1-1c. (Yield 68%)
[0098] (2) Compound 1-1
##STR00024##
[0099] In the 500 mL reactor, the compound I1-1c 6.3 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.3
g of the compound 1-1. (Yield 21%)
[0100] 2. Synthesis of Compound 1-2
[0101] (1) Compound I1-2c
##STR00025##
[0102] In the 500 mL reactor, the compound I1-2a 8.5 g (50 mmol),
the compound I1-2b 18.6 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred/refluxed for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 16.9 g of the
compound I1-2c. (Yield 67%)
[0103] (2) Compound 1-2
##STR00026##
[0104] In the 500 mL reactor, the compound I1-2c 6.3 g (12.5 mmol)
and tert-butylbenzene 60 mL were added to a 500 mL reactor. 45 mL
(37.5 mmol) of n-butyllithium was dropwisely added at -78.degree.
C. After dropwise addition, the mixture was stirred at 60.degree.
C. for 3 hours. Then, nitrogen was blown at 60.degree. C. to remove
heptane. Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.1
g of the compound 1-2. (Yield 19%)
[0105] 3. Synthesis of Compound 1-4
[0106] (1) Compound I1-4c
##STR00027##
[0107] In the 500 mL reactor, the compound I1-4a 8.5 g (50 mmol),
the compound I1-4b 19.4 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred/refluxed for 5 hours. After completion of the
reaction, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 13.5 g of the
compound I1-4c. (Yield 52%)
[0108] (2) Compound 1-4
##STR00028##
[0109] In the 500 mL reactor, the compound I1-4c 6.5 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 0.9
g of the compound 1-4. (Yield 15%)
[0110] 4. Synthesis of Compound 1-7
[0111] (1) Compound I1-7c
##STR00029##
[0112] In the 500 mL reactor, the compound I1-7a 8.5 g (50 mmol),
the compound I1-7b 19.4 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred/refluxed for 5 hours. After completion of the
reaction, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 16.9 g of the
compound I1-7c. (Yield 65%)
[0113] (2) Compound 1-7
##STR00030##
[0114] In the 500 mL reactor, the compound I1-7c 6.5 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.2
g of the compound 1-7. (Yield 20%)
[0115] 5. Synthesis of Compound 1-8
[0116] (1) Compound I1-8c
##STR00031##
[0117] In the 500 mL reactor, the compound I1-8a 8.5 g (50 mmol),
the compound I1-8b 18.6 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred/refluxed for 5 hours. After completion of the
reaction, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 16.7 g of the
compound I1-8c. (Yield 66%)
[0118] (2) Compound 1-8
##STR00032##
[0119] In the 500 mL reactor, the compound I1-8c 6.3 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.1
g of the compound 1-8. (Yield 18%)
[0120] 6. Synthesis of Compound 1-9
[0121] (1) Compound I1-9c
##STR00033##
[0122] In the 500 mL reactor, the compound I1-9a 8.5 g 50 mmol), t
e compound I1-9b 19.4 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.5 g of the
compound I1-9c. (Yield 71%)
[0123] (2) Compound 1-9
##STR00034##
[0124] In the 500 mL reactor, the compound I1-9c 6.5 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 1-9. (Yield 23%)
[0125] 7. Synthesis of Compound 2-1
[0126] (1) Compound I2-1c
##STR00035##
[0127] In the 500 mL reactor, the compound I2-1a 8.5 g (50 mmol),
the compound I2-1b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After completion of the
reaction, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 17.7 g of the
compound I2-1c. (Yield 64%)
[0128] (2) Compound 2-1
##STR00036##
[0129] In the 500 mL reactor, the compound 12-1c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.2
g of the compound 2-1. (Yield 18%)
[0130] 8. Synthesis of Compound 2-2
[0131] (1) Compound 12-2c
##STR00037##
[0132] In the 500 mL reactor, the compound 12-2a 8.5 g (50 mmol),
the compound 12-2b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.0 g of the
compound 12-2c. (Yield 65%)
[0133] (2) Compound 2-2
##STR00038##
[0134] In the 500 mL reactor, the compound 12-2c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added to. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.1
g of the compound 2-2. (Yield 16%)
[0135] 9. Synthesis of Compound 2-3
[0136] (1) Compound 12-3c
##STR00039##
[0137] In the 500 mL reactor, the compound 12-3a 8.5 g (50 mmol),
the compound 12-3b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.3 g of the
compound 12-3c. (Yield 66%)
[0138] (2) Compound 2-3
##STR00040##
[0139] In the 500 mL reactor, the compound 12-3c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.3
g of the compound 2-3. (Yield 19%)
[0140] 10. Synthesis of Compound 2-4
[0141] (1) Compound 12-4c
##STR00041##
[0142] In the 500 mL reactor, the compound 12-4a 8.5 g (50 mmol),
the compound 12-4b 21.9 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.5 g of the
compound 12-4c. (Yield 65%)
[0143] (2) Compound 2-4
##STR00042##
[0144] In the 500 mL reactor, the compound 12-4c 7.1 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 2-4. (Yield 20%)
[0145] 11. Synthesis of Compound 2-6
[0146] (1) Compound 12-6c
##STR00043##
[0147] In the 500 mL reactor, the compound 12-6a 8.5 g (50 mmol),
the compound 12-6b 21.9 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.5 g of the
compound 12-6c. (Yield 65%)
[0148] (2) Compound 2-6
##STR00044##
[0149] In the 500 mL reactor, the compound I2-6c 7.1 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.6
g of the compound 2-6. (Yield 24%)
[0150] 12. Synthesis of Compound 3-1
[0151] (1) Compound I3-1c
##STR00045##
[0152] In the 500 mL reactor, the compound I3-1a 8.5 g (50 mmol),
the compound I3-1b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 17.5 g of the
compound I3-1c. (Yield 63%)
[0153] (2) Compound 3-1
##STR00046##
[0154] In the 500 mL reactor, the compound I3-1c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 3-1. (Yield 21%)
[0155] 13. Synthesis of Compound 3-4
[0156] (1) Compound I3-4c
##STR00047##
[0157] In the 500 mL reactor, the compound I3-4a 8.5 g (50 mmol),
the compound I3-4b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.6 g of the
compound I3-4c. (Yield 67%)
[0158] (2) Compound 3-4
##STR00048##
[0159] In the 500 mL reactor, the compound I3-4c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.3
g of the compound 3-4. (Yield 19%)
[0160] 14. Synthesis of Compound 3-7
[0161] (1) Compound I3-7c
##STR00049##
[0162] In the 500 mL reactor, the compound I3-7a 8.5 g (50 mmol),
the compound I3-7b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 17.8 g of the
compound I3-7c. (Yield 64%)
[0163] (2) Compound 3-7
##STR00050##
[0164] In the 500 mL reactor, the compound I3-7c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 3-7. (Yield 21%)
[0165] 15. Synthesis of Compound 3-8
[0166] (1) Compound I3-8c
##STR00051##
[0167] In the 500 mL reactor, the compound I3-8a 8.5 g (50 mmol),
the compound I3-8b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 18.3 g of the
compound I3-8c. (Yield 66%)
[0168] (2) Compound 3-8
##STR00052##
[0169] In the 500 mL reactor, the compound I3-8c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.3
g of the compound 3-8. (Yield 20%)
[0170] 16. Synthesis of Compound 3-9
[0171] (1) Compound I3-9c
##STR00053##
[0172] In the 500 mL reactor, the compound I3-9a 8.5 g (50 mmol),
the compound I3-9b 21.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 19.1 g of the
compound I3-9c. (Yield 69%)
[0173] (2) Compound 3-9
##STR00054##
[0174] In the 500 mL reactor, the compound I3-9c 6.9 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.1
g of the compound 3-9. (Yield 17%)
[0175] 17. Synthesis of Compound 4-1
[0176] (1) Compound I4-1c
##STR00055##
[0177] In the 500 mL reactor, the compound I4-1a 8.5 g (50 mmol),
the compound I4-1b 23.6 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 17.8 g of the
compound I4-1c. (Yield 59%)
[0178] (2) Compound 4-1
##STR00056##
[0179] In the 500 mL reactor, the compound I4-1c 7.6 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropyl ethyl amine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 4-1. (Yield 19%)
[0180] 18. Synthesis of Compound 4-3
[0181] (1) Compound I4-3c
##STR00057##
[0182] In the 500 mL reactor, the compound I4-3a 8.5 g (50 mmol),
the compound I4-3b 23.6 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 20.5 g of the
compound I4-3c. (Yield 68%)
[0183] (2) Compound 4-3
##STR00058##
[0184] In the 500 mL reactor, the compound I4-3c 7.6 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.6
g of the compound 4-3. (Yield 22%)
[0185] 19. Synthesis of Compound 4-4
[0186] (1) Compound I4-4c
##STR00059##
[0187] In the 500 mL reactor, the compound I4-4a 8.5 g (50 mmol),
the compound I4-4b 23.6 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 20.8 g of the
compound I4-4c. (Yield 69%)
[0188] (2) Compound 4-4
##STR00060##
[0189] In the 500 mL reactor, the compound I4-4c 7.6 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 4-4. (Yield 19%)
[0190] 20. Synthesis of Compound 4-7
[0191] (1) Compound I4-7c
##STR00061##
[0192] In the 500 mL reactor, the compound I4-7a 35.9 g (110 mmol),
the compound I4-7b 9.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 26.6 g of the
compound I4-7c. (Yield 70%)
[0193] (2) Compound 4-7
##STR00062##
[0194] In the 500 mL reactor, the compound I4-7c 9.5 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.5
g of the compound 4-7. (Yield 16%)
[0195] 21. Synthesis of Compound 4-8
[0196] (1) Compound I4-8c
##STR00063##
[0197] In the 500 mL reactor, the compound I4-8a 35.9 g (110 mmol),
the compound I4-8b 9.1 g (50 mmol), palladium acetate 0.45 g (2
mmol), sodium tert-butoxide 18.9 g (196 mmol),
tri-tert-butylphosphine 0.8 g (4 mmol) and 300 mL of toluene were
added and stirred under reflux for 5 hours. After the reaction was
completed, the resultant was filtered and concentrated. The mixture
was separated by column chromatography to obtain 25.9 g of the
compound I4-8c. (Yield 68%)
[0198] (2) Compound 4-8
##STR00064##
[0199] In the 500 mL reactor, the compound I4-8c 9.5 g (12.5 mmol)
and tert-butylbenzene 60 mL were added. 45 mL (37.5 mmol) of
n-butyllithium was dropwisely added at -78.degree. C. After
dropwise addition, the mixture was stirred at 60.degree. C. for 3
hours. Then, nitrogen was blown at 60.degree. C. to remove heptane.
Boron tribromide 6.3 g (25 mmol) was dropwisely added at
-78.degree. C. After the dropwise addition, the mixture was stirred
at room temperature for 1 hour, and 3.2 g (25 mmol) of
N,N-diisopropylethylamine was dropwisely added at 0.degree. C.
After dropwise addition, the mixture was stirred at 120.degree. C.
for 2 hours. After the reaction was completed, an aqueous sodium
acetate solution was added thereto and stirred at room temperature.
The mixture was extracted with ethyl acetate, the organic layer was
concentrated, and separated by column chromatography to obtain 1.4
g of the compound 4-8. (Yield 15%)
[0200] In the EML 240, the first compound 242 acts as a dopant
(emitter) to emit the blue light.
[0201] In addition, the EML 240 may further include a second
compound 244 as a host. In this instance, in the EML 240, the first
compound 242 may have a weight % of about 0.1 to 30, or about 0.1
to 10, and alternatively about 1 to 5. The EML 240 may have a
thickness of about 10 to 500 .ANG., or about 50 to 400 .ANG., and
alternatively about 100 to 300 .ANG..
[0202] The second compound 244 as the host may be an anthracene
derivative. For example, the second compound 244 may be represented
by Formula 7.
##STR00065##
[0203] In Formula 7, each of Ar.sub.1 and Ar.sub.2 is independently
C6 to C30 aryl group or C5 to C30 heteroaryl group. L is a single
bond or C6 to C30 arylene group. In this instance, hydrogens in the
anthracene derivative are not deuterated or partially or wholly
deuterated. Namely, none, a part or all of the hydrogens in the
anthracene derivative is substituted by deuterium.
[0204] In Formula 7, each of Ar.sub.1 and Ar.sub.2 may be selected
from the group consisting of phenyl, naphthyl, dibenzofuranyl and
fused dibenzofuranyl, and L may be the single bond or
phenylene.
[0205] For example, Ar.sub.1 may be selected from the group
consisting of naphthyl, dibenzofuranyl, phenyl-dibenzofuranyl and
fused dibenzofuranyl, and Ar.sub.2 may be selected from the group
consisting of phenyl and naphthyl. In an aspect, Ar.sub.1 and
Ar.sub.2 may be naphthyl, and L may be the single bond or
phenylene.
[0206] In Formula 7, the anthracene core may be partially or wholly
deuterated, or each of Ar.sub.1, Ar.sub.2, L may be partially or
wholly deuterated. Alternatively, each of the anthracene core,
Ar.sub.1, Ar.sub.2, L may be partially or wholly deuterated.
[0207] The second compound 244 in Formula 7 may be one of compounds
in Formula 8.
##STR00066## ##STR00067##
[0208] The HIL 210 may include at least one compound selected from
the group consisting of
4,4',4''-tris(3-methylphenylamino)triphenylamine (MTDATA),
4,4',4''-tris(N,N-diphenyl-amino)triphenylamine (NATA),
4,4',4''-tris(N-(naphthalene-1-yl)-N-phenyl-amino)triphenylamine
(1T-NATA),
4,4',4''-tris(N-(naphthalene-2-yl)-N-phenyl-amino)triphenylamine
(2T-NATA), copper phthalocyanine (CuPc),
tris(4-carbazoyl-9-yl-phenyl)amine (TCTA),
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4''-diamine (NPB
or NPD),
1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile(dipyrazino2,3-f:2'-
3'-hquinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN),
1,3,5-tris4-(diphenylamino)phenylbenzene (TDAPB),
poly(3,4-ethylenedioxythiphene)polystyrene sulfonate (PEDOT/PSS),
and
N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-
-fluoren-2-amine. Alternatively, the HIL 210 may include a compound
in Formula 15 as a host and a compound in Formula 16 as a
dopant.
[0209] The HTL 220 may include at least one compound selected from
the group consisting of
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine
(TPD), NPB (or NPD), 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP),
polyN,N'-bis(4-butylpnehyl)-N,N'-bis(phenyl)-benzidine (poly-TPD),
(poly(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphe-
nylamine)) (TFB), di-4-(N,N-di-p-tolyl-amino)-phenylcyclohexane
(TAPC), 3,5-di(9H-carbazol-9-yl)-N,N-diphenylaniline (DCDPA),
N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-
-fluoren-2-amine, and
N-(biphenyl-4-yl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)biphenyl-4-amine-
. Alternatively, the HTL 220 may include a compound of Formula
15.
[0210] The EBL 230, which is disposed between the HTL 220 and the
EML 240, is formed to prevent the electron toward the HTL 220. The
EBL 230 includes the electron blocking material of the amine
derivative. The electron blocking material is represented by
Formula 9.
##STR00068##
[0211] In Formula 9, L is C6 to C30 arylene group, and a is 0 or 1.
Each of R.sub.1 and R.sub.2 is independently selected from the
group consisting of C6 to C30 aryl group and C5 to C30 heteroaryl
group.
[0212] For example, L may be phenylene, and each of R.sub.1 and
R.sub.2 may be selected from the group consisting of biphenyl,
fluorenyl, carbazolyl, phenylcarbazolyl, carbazolylphenyl,
dibenzothiophenyl and dibenzofuranyl.
[0213] Namely, the electron blocking material may be an amine
derivative substituted by spirofluorene (e.g.,
"spirofluorene-substituted amine derivative").
[0214] The electron blocking material of Formula 9 may be one of
the followings of Formula 10:
##STR00069## ##STR00070## ##STR00071## ##STR00072##
[0215] The HBL 250, which is disposed between the EML 240 and the
EIL, 260, is formed to prevent the hole toward the EIL, 260. The
HBL 250 includes the hole blocking material of the azine
derivative. The azine derivative as the hole blocking material is
represented by Formula 11.
##STR00073##
[0216] In Formula 11, each of Y.sub.1 to Y.sub.5 is independently
CR.sub.1 or N, and one to three of Y.sub.1 to Y.sub.5 is N. R.sub.1
is independently C6.about.C.sub.30 aryl group. L is
C6.about.C.sub.30 arylene group, and R.sub.2 is C6.about.C.sub.30
aryl group or C5.about.C.sub.30 hetero aryl group. R.sub.3 is
hydrogen, or adjacent two of R.sub.3 form a fused ring. "a" is 0 or
1, "b" is 1 or 2, and "c" is an integer of 0 to 4.
[0217] The hole blocking material of Formula 11 may be one of the
followings of Formula 12.
##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078##
##STR00079## ##STR00080##
[0218] Alternatively, the HBL 250 may include the benzimidazole
derivative as the hole blocking material. For example, the
benzimidazole derivative as the hole blocking material is
represented by Formula 13.
##STR00081##
[0219] In Formula 13, Ar is C.sub.10.about.C.sub.30 arylene group,
R.sub.1 is C.sub.6.about.C.sub.30 aryl group or
C.sub.5.about.C.sub.30 hetero aryl group, and R.sub.2 is hydrogen,
C.sub.1.about.C.sub.10 alkyl group or C.sub.6.about.C.sub.30 aryl
group.
[0220] For example, Ar may be naphthylene or anthracenylene,
R.sub.1 may be benzimidazole or phenyl, and R.sub.2 may be methyl,
ethyl or phenyl.
[0221] The hole blocking material of Formula 13 may be one of the
followings of Formula 14.
##STR00082## ##STR00083##
[0222] The HBL 250 may include at least one of the hole blocking
material in Formula 11 and the hole blocking material in Formula
13.
[0223] In this instance, a thickness of EML 240 may be greater than
each of that of the EBL 230 and the HBL 250 and may be smaller than
that of the HTL 220. For example, the EML 240 may have a thickness
of about 150 to 250 .ANG., each of the EBL 230 and the HBL 250 may
have a thickness of about 50 to 150 .ANG., and the HTL 220 may have
a thickness of about 900 to 1100 .ANG.. The EBL 230 and the HBL 250
may have the same thickness.
[0224] The HBL 250 may include the compound in Formula 11 and the
compound in Formula 13. For example, in the HBL 250, the compound
in Formula 11 and the compound in Formula 13 may have the same
weight %.
[0225] In this instance, a thickness of the EML 240 may be greater
than that of the EBL 250 and may be smaller than that of the HBL
250. In addition, the thickness of the HBL 250 may be smaller than
that of the HTL 220. For example, the EML 240 may have a thickness
of about 200 to 300 .ANG., and the EBL may have a thickness of
about 50 to 150 .ANG.. The HBL 250 may have a thickness of about
250 to 350 .ANG., and the HTL 220 may have a thickness of about 800
to 1000 .ANG..
[0226] The electron blocking material in Formula 11 and/or Formula
13 has excellent hole blocking property and excellent electron
transporting property. Accordingly, an electron transporting layer
may be presented, and the HBL 250 may directly contact the HIL 260
or the second electrode 164.
[0227] The EIL 260 may include at least one of an alkali metal,
such as Li, an alkali halide compound, such as LiF, CsF, NaF, or
BaF.sub.2, and an organo-metallic compound, such as Liq, lithium
benzoate, or sodium stearate, but it is not limited thereto.
Alternatively, the EIL 260 may include a compound of Formula 17 as
a host and an alkali metal as a dopant.
[0228] In the OLED D, the EML 240 includes the emitting compound
242 in Formula 1 such that the lifespan of the OLED D and the
organic light emitting display device 100 is significantly
improved.
[Organic Light Emitting Diode]
[0229] The anode (ITO, 0.5 mm), the HIL (Formula 15 (97 wt %) and
Formula 16 (3 wt %), 100 .ANG.), the HTL (Formula 15, 1000 .ANG.),
the EBL (the compound EBL-11 in Formula 10, 100 .ANG.), the EML
(the compound H-1 in Formula 8 (host, 98 wt %) and dopant (2 wt %),
200 .ANG.), the HBL (the compound E1 in Formula 12, 100 .ANG.), the
EIL (Formula 17 (98 wt %) and Li (2 wt %), 200 .ANG.) and the
cathode (Al, 500 .ANG.) was sequentially deposited. An
encapsulation film is formed by using an UV curable epoxy and a
moisture getter to form the OLED.
##STR00084##
(1) Comparative Examples 1 and 2 (Ref1 and Ref2)
[0230] The compound "Ref-1" in Formula 18 and the compound "Ref-2"
in Formula 19 are respectively used as the dopant to form the
EML.
(2) Examples 1 to 2l (Ex1 to Ex21)
[0231] The compounds 1-1, 1-2, 1-4, 1-7 to 1-9, 2-1 to 2-4, 2-6,
3-1, 3-4, 3-7 to 3-9, 4-1, 4-3, 4-4, 4-7 and 4-9 in Formula 6 are
respectively used as the dopant to form the EML.
##STR00085##
[0232] The properties, i.e., voltage (V), external quantum
efficiency (EQE), color coordinate (CIE) and lifespan (T.sub.95),
of the OLEDs manufactured in Comparative Examples 1 and 2 and
Examples 1 to 21 are measured and listed in Tables 1 and 2. The
properties of the OLED were measured at the room temperature using
a current source (KEITHLEY) and a photometer (PR 650). The driving
voltage, the external quantum efficiency, and the color coordinate
were measured under the condition of a current density of 10
mA/cm.sup.2, and the lifespan was measured at 40.degree. C. and the
time to reach 95% of the lifespan under the 22.5 mA/cm.sup.2
condition.
TABLE-US-00001 TABLE 1 Dopant V EQE (%) CIE(x, y) T.sub.95 (hr)
Ref1 Ref-1 3.95 6.31 (0.140, 0.060) 76 Ref2 Ref-2 3.94 6.28 (0.140,
0.075) 72 Ex1 1-1 3.93 6.42 (0.141, 0.128) 115 Ex2 1-2 3.94 6.25
(0.140, 0.121) 109 Ex3 1-4 3.91 6.21 (0.140, 0.120) 114 Ex4 1-7
3.91 6.35 (0.140, 0.123) 120 Ex5 1-8 3.90 5.99 (0.141, 0.120) 115
Ex6 1-9 3.97 6.08 (0.140, 0.119) 103 Ex7 2-1 3.95 6.15 (0.140,
0.078) 105 Ex8 2-2 3.96 6.32 (0.140, 0.186) 111 Ex9 2-3 3.92 6.75
(0.141, 0.129) 117 Ex10 2-4 3.88 6.66 (0.140, 0.079) 101 Ex11 2-6
3.90 6.49 (0.142, 0.125) 105
TABLE-US-00002 TABLE 2 Dopant V EQE (%) CIE(x, y) T.sub.95 (hr)
Ex12 3-1 3.99 6.38 (0.141, 0.071) 110 Ex13 3-4 3.98 6.47 (0.140,
0.178) 106 Ex14 3-7 3.96 5.72 (0.140, 0.046) 108 Ex15 3-8 3.98 5.44
(0.141, 0.045) 102 Ex16 3-9 4.01 5.51 (0.140, 0.046) 99 Ex17 4-1
3.88 6.28 (0.140, 0.055) 111 Ex18 4-3 3.89 6.29 (0.140, 0.087) 114
Ex19 4-4 3.92 6.45 (0.141, 0.115) 109 Ex20 4-7 3.91 6.50 (0.140,
0.095) 102 Ex21 4-8 3.91 6.42 (0.140, 0.127) 118
[0233] As shown in Tables 1 and 2, in comparison to the OLED of
Ref1 and Ref2, the lifespan of the OLED in Ex1 to Ex21 using the
emitting compound of the present disclosure as the dopant is
significantly improved.
[0234] Particularly, as seen from Examples 1, 3 to 5, and 12 to 14,
when the compounds 1-1, 1-4, 1-7, 1-8, 3-1, 3-4 and 3-7, in which
the carbon atom being adjacent to the nitrogen atom is substituted
by D-substituted alkyl group, e.g., CD.sub.3, are used as the
dopant, the lifespan of the OLED is further increased.
[0235] In addition, as seen from Examples 8, 9 and 11, when the
compounds 2-2, 2-3 and 2-6, in which the carbon atom being adjacent
to the hetero-atom in the five-membered ring is substituted by
D-substituted alkyl group, e.g., CD.sub.3, are used as the dopant,
the lifespan of the OLED is further increased.
[0236] FIG. 4 is a schematic cross-sectional view illustrating an
OLED having a tandem structure of two emitting units for the
organic light emitting display device according to the first aspect
of the present disclosure.
[0237] As shown in FIG. 4, the OLED D includes the first and second
electrodes 160 and 164 facing each other and the organic emitting
layer 162 between the first and second electrodes 160 and 164. The
organic emitting layer 162 includes a first emitting part 310
including a first EML 320, a second emitting part 330 including a
second EML 340 and a charge generation layer (CGL) 350 between the
first and second emitting parts 310 and 330. The organic light
emitting display device 100 (of FIG. 2) includes a red pixel, a
green pixel and a blue pixel, and the OLED D is positioned in the
blue pixel.
[0238] One of the first and second electrodes 160 and 164 is an
anode, and the other one of the first and second electrodes 160 and
164 is cathode. In addition, one of the first and second electrodes
160 and 164 may be a transparent (or a semi-transparent) electrode,
and the other one of the first and second electrodes 160 and 164
may be a reflection electrode.
[0239] The CGL 350 is positioned between the first and second
emitting parts 310 and 330, and the first emitting part 310, the
CGL 350 and the second emitting part 330 are sequentially stacked
on the first electrode 160. Namely, the first emitting part 310 is
positioned between the first electrode 160 and the CGL 350, and the
second emitting part 320 is positioned between the second electrode
160 and the CGL 350.
[0240] The first emitting part 310 includes a first EML 320. In
addition, the first emitting part 310 may further include a first
EBL 316 between the first electrode 160 and the first EML 320 and a
first HBL 318 between the first EML 320 and the CGL 350.
[0241] In addition, the first emitting part 310 may further include
a first HTL 314 between the first electrode 160 and the first EBL
316 and an HIL 312 between the first electrode 160 and the first
HTL 314.
[0242] The first EML 320 includes the emitting compound in Formula
1 as a first compound 322 and provides blue emission. For example,
the first compound 322 in the first EML 320 may be one of the
compounds in Formula 6.
[0243] The EML 320 may further include a second compound 324. For
example, the second compound 324 may be represented by Formula 7
and may be one of the compounds in Formula 8.
[0244] In the first EML 320, the first compound 322 has a weight %
being smaller than the second compound 324. The first compound 322
may act as a dopant (an emitter), and the second compound 324 may
act as a host. For example, in the first EML 320, the first
compound 322 may have a weight % of about 0.1 to 30. To provide
sufficient emitting efficiency and lifespan, the weight % of the
first compound 322 may be about 0.1 to 10, or about 1 to 5.
[0245] The first EBL 316 may include the compound in Formula 9 as
the electron blocking material. In addition, the first HBL 318 may
include at least one of the compounds in Formula 11 and Formula 13
as the hole blocking material.
[0246] The second emitting part 330 includes the second EML 340. In
addition, the second emitting part 330 may further include a second
EBL 334 between the CGL 350 and the second EML 340 and a second HBL
336 between the second EML 340 and the second electrode 164.
[0247] In addition, the second emitting part 330 may further
include a second HTL 332 between the CGL 350 and the second EBL 334
and an EIL 338 between the second HBL 336 and the second electrode
164.
[0248] The second EML 340 includes the emitting compound in Formula
1 as a third compound 342 and provides blue emission. For example,
the third compound 342 in the second EML 340 may be one of the
compounds in Formula 6.
[0249] The second EML 340 may further include a fourth compound
344. For example, the fourth compound 344 may be represented by
Formula 7 and may be one of the compounds in Formula 8.
[0250] In the second EML 340, the third compound 342 may have a
weight % being less than the fourth compound 344. In the second EML
340, the third compound 342 may act as a dopant (an emitter), and
the fourth compound 344 may act as a host. For example, in the
second EML 340, the third compound 342 has a weight % of about 0.1
to 30. To provide sufficient emitting efficiency and lifespan, the
weight % of the third compound 342 may be about 0.1 to 10, or about
1 to 5.
[0251] The third compound 342 in the second EML 340 and the first
compound 322 in the first EML 320 may be same or different, and the
fourth compound 344 in the second EML 340 and the second compound
324 in the first EML 320 may be same or different. In addition, the
weight % of the first compound 322 in the first EML 320 and the
weight % of the third compound 342 in the second EML 340 may be
same or different.
[0252] The second EBL 334 may include the electron blocking
material in Formula 9. In addition, the second HBL 336 may include
at least one of the hole blocking material in Formula 11 and the
hole blocking material in Formula 13.
[0253] The CGL 350 is positioned between the first and second
emitting parts 310 and 330. Namely, the first and second emitting
parts 310 and 330 are connected through the CGL 350. The CGL 350
may be a P-N junction CGL of an N-type CGL 352 and a P-type CGL
354.
[0254] The N-type CGL 352 is positioned between the first HBL 318
and the second HTL 332, and the P-type CGL 354 is positioned
between the N-type CGL 352 and the second HTL 332.
[0255] In the OLED D, since each of the first and second EMLs 320
and 340 includes the emitting compound in Formula 1 as the first
and third compounds 322 and 342, respectively, the emitting
efficiency and the lifespan of the OLED D and the organic light
emitting display device 100 are improved.
[0256] In addition, since the first and second emitting parts 310
and 330 for emitting blue light are stacked, the organic light
emitting display device 100 provides an image having high color
temperature.
[0257] FIG. 5 is a schematic cross-sectional view illustrating an
organic light emitting display device according to a second aspect
of the present disclosure, and FIG. 6 is a schematic
cross-sectional view illustrating an OLED having a tandem structure
of two emitting parts for the organic light emitting display device
according to the second aspect of the present disclosure. FIG. 7 is
a schematic cross-sectional view illustrating an OLED having a
tandem structure of three emitting parts for the organic light
emitting display device according to the second aspect of the
present disclosure.
[0258] As shown in FIG. 5, the organic light emitting display
device 400 includes a first substrate 410, where a red pixel BP, a
green pixel GP and a blue pixel BP are defined, a second substrate
470 facing the first substrate 410, an OLED D, which is positioned
between the first and second substrates 410 and 470 and providing
white emission, and a color filter layer 480 between the OLED D and
the second substrate 470.
[0259] Each of the first and second substrates 410 and 470 may be a
glass substrate or a flexible substrate. For example, each of the
first and second substrates 410 and 470 may be a polyimide (PI)
substrate, a polyethersulfone (PES) substrate, a
polyethylenenaphthalate (PEN) substrate, a polyethylene
terephthalate (PET) substrate or a polycarbonate (PC)
substrate.
[0260] A buffer layer 420 is formed on the substrate, and the TFT
Tr corresponding to each of the red, green and blue pixels RP, GP
and BP is formed on the buffer layer 420. The buffer layer 420 may
be omitted.
[0261] A semiconductor layer 422 is formed on the buffer layer 420.
The semiconductor layer 422 may include an oxide semiconductor
material or polycrystalline silicon.
[0262] A gate insulating layer 424 is formed on the semiconductor
layer 422. The gate insulating layer 424 may be formed of an
inorganic insulating material such as silicon oxide or silicon
nitride.
[0263] A gate electrode 430, which is formed of a conductive
material, e.g., metal, is formed on the gate insulating layer 424
to correspond to a center of the semiconductor layer 422.
[0264] An interlayer insulating layer 432, which is formed of an
insulating material, is formed on the gate electrode 430. The
interlayer insulating layer 432 may be formed of an inorganic
insulating material, e.g., silicon oxide or silicon nitride, or an
organic insulating material, e.g., benzocyclobutene or
photo-acryl.
[0265] The interlayer insulating layer 432 includes first and
second contact holes 434 and 436 exposing both sides of the
semiconductor layer 422. The first and second contact holes 434 and
436 are positioned at both sides of the gate electrode 430 to be
spaced apart from the gate electrode 430.
[0266] A source electrode 440 and a drain electrode 442, which are
formed of a conductive material, e.g., metal, are formed on the
interlayer insulating layer 432.
[0267] The source electrode 440 and the drain electrode 442 are
spaced apart from each other with respect to the gate electrode 430
and respectively contact both sides of the semiconductor layer 422
through the first and second contact holes 434 and 436.
[0268] The semiconductor layer 422, the gate electrode 430, the
source electrode 440 and the drain electrode 442 constitute the TFT
Tr. The TFT Tr serves as a driving element. Namely, the TFT Tr may
correspond to the driving TFT Td (of FIG. 1).
[0269] Although not shown, the gate line and the data line cross
each other to define the pixel, and the switching TFT is formed to
be connected to the gate and data lines. The switching TFT is
connected to the TFT Tr as the driving element.
[0270] In addition, the power line, which may be formed to be
parallel to and spaced apart from one of the gate and data lines,
and the storage capacitor for maintaining the voltage of the gate
electrode of the TFT Tr in one frame may be further formed.
[0271] A passivation layer 450, which includes a drain contact hole
452 exposing the drain electrode 442 of the TFT Tr, is formed to
cover the TFT Tr.
[0272] A first electrode 460, which is connected to the drain
electrode 442 of the TFT Tr through the drain contact hole 452, is
separately formed in each pixel and on the passivation layer 450.
The first electrode 460 may be an anode and may be formed of a
conductive material, e.g., a transparent conductive oxide (TCO),
having a relatively high work function. For example, the first
electrode 460 may be formed of indium-tin-oxide (ITO),
indium-zinc-oxide (IZO), indium-tin-zinc-oxide (ITZO), tin oxide
(SnO), zinc oxide (ZnO), indium-copper-oxide (ICO) or
aluminum-zinc-oxide (Al:ZnO, AZO).
[0273] When the organic light emitting display device 400 is
operated in a bottom-emission type, the first electrode 460 may
have a single-layered structure of the transparent conductive
material layer. When the Organic light emitting display device 400
is operated in a top-emission type, a reflection electrode or a
reflection layer may be formed under the first electrode 160. For
example, the reflection electrode or the reflection layer may be
formed of silver (Ag) or aluminum-palladium-copper (APC) alloy. In
this instance, the first electrode 460 may have a triple-layered
structure of ITO/Ag/ITO or ITO/APC/ITO.
[0274] A bank layer 466 is formed on the passivation layer 450 to
cover an edge of the first electrode 460. Namely, the bank layer
466 is positioned at a boundary of the pixel and exposes a center
of the first electrode 460 in the pixel. Since the OLED D emits the
white light in the red, green and blue pixels RP, GP and BP, the
organic emitting layer 162 may be formed as a common layer in the
red, green and blue pixels RP, GP and BP without separation. The
bank layer 466 may be formed to prevent a current leakage at an
edge of the first electrode 460 and may be omitted.
[0275] An organic emitting layer 462 is formed on the first
electrode 460.
[0276] Referring to FIG. 6, the OLED D includes the first and
second electrodes 460 and 464 facing each other and the organic
emitting layer 462 between the first and second electrodes 460 and
464. The organic emitting layer 462 includes a first emitting part
710 including a first EML 720, a second emitting part 730 including
a second EML 740 and a charge generation layer (CGL) 750 between
the first and second emitting parts 710 and 730.
[0277] The first electrode 460 may be formed of a conductive
material having a relatively high work function to serve as an
anode for injecting a hole into the organic emitting layer 462. The
second electrode 464 may be formed of a conductive material having
a relatively low work function to serve as a cathode for injecting
an electron into the organic emitting layer 462.
[0278] The CGL 750 is positioned between the first and second
emitting parts 710 and 730, and the first emitting part 710, the
CGL 750 and the second emitting part 730 are sequentially stacked
on the first electrode 460. Namely, the first emitting part 710 is
positioned between the first electrode 460 and the CGL 750, and the
second emitting part 720 is positioned between the second electrode
460 and the CGL 750.
[0279] The first emitting part 710 includes a first EML 720. In
addition, the first emitting part 710 may further include a first
EBL 716 between the first electrode 460 and the first EML 720 and a
first HBL 718 between the first EML 720 and the CGL 750.
[0280] In addition, the first emitting part 710 may further include
a first HTL 714 between the first electrode 460 and the first EBL
716 and an HIL 712 between the first electrode 460 and the first
HTL 714.
[0281] The first EML 720 includes the emitting compound in Formula
1 as a first compound 722 and provides blue emission. For example,
the first compound 722 in the first EML 720 may be one of the
compounds in Formula 6.
[0282] The EML 720 may further include a second compound 724. For
example, the second compound 724 may be represented by Formula 7
and may be one of the compounds in Formula 8.
[0283] In the first EML 720, the first compound 722 has a weight %
being smaller than the second compound 724. The first compound 722
may act as a dopant (an emitter), and the second compound 724 may
act as a host. For example, in the first EML 720, the first
compound 722 may have a weight % of about 0.1 to 30. To provide
sufficient emitting efficiency and lifespan, the weight % of the
first compound 722 may be about 0.1 to 10, or about 1 to 5.
[0284] The first EBL 716 may include the compound in Formula 9 as
the electron blocking material. In addition, the first HBL 718 may
include at least one of the compounds in Formula 11 and Formula 13
as the hole blocking material.
[0285] The second emitting part 730 includes the second EML 740. In
addition, the second emitting part 730 may further include a second
EBL 734 between the CGL 750 and the second EML 740 and a second HBL
736 between the second EML 740 and the second electrode 464.
[0286] In addition, the second emitting part 730 may further
include a second HTL 732 between the CGL 750 and the second EBL 734
and an EIL 738 between the second HBL 736 and the second electrode
464.
[0287] The second EML 740 may be a yellow-green EML. For example,
the second EML 740 may include a yellow-green dopant 743 and a host
745. The yellow-green dopant 743 may be one of a yellow-green
fluorescent compound, a yellow-green phosphorescent compound and a
yellow-green delayed fluorescent compound.
[0288] In the second EML 740, the host 745 may have a weight % of
about 70 to 99.9, and the yellow-green dopant 743 may have a weight
% of about 0.1 to 30. To provide sufficient emitting efficiency,
the yellow-green dopant 744 may have a weight % of about 0.1 to 10,
or about 1 to 5.
[0289] The second EBL 734 may include the compound in Formula 9 as
the electron blocking material. In addition, the second HBL 736 may
include at least one of the compounds in Formula 11 and Formula 13
as the hole blocking material.
[0290] The CGL 750 is positioned between the first and second
emitting parts 710 and 730. Namely, the first and second emitting
parts 710 and 730 are connected through the CGL 750. The CGL 750
may be a P-N junction CGL of an N-type CGL 752 and a P-type CGL
754.
[0291] The N-type CGL 752 is positioned between the first HBL 718
and the second HTL 732, and the P-type CGL 754 is positioned
between the N-type CGL 752 and the second HTL 732.
[0292] In FIG. 6, the first EML 720, which is positioned between
the first electrode 460 and the CGL 750, includes the first
compound 722 being the emitting compound of the present disclosure
and the second compound 724 being the anthracene derivative, and
the second EML 740, which is positioned between the second
electrode 464 and the CGL 750, is the yellow-green EML.
Alternatively, the first EML 720, which is positioned between the
first electrode 460 and the CGL 750, may be the yellow-green EML,
and the second EML 740, which is positioned between the second
electrode 464 and the CGL 750, may include the emitting compound of
the present disclosure and the anthracene derivative to be a blue
EML.
[0293] In the OLED D, since the first EML 720 includes the emitting
compound 722 of the present disclosure such that the emitting
efficiency and the lifespan of the OLED D and the organic light
emitting display device 400 are significantly improved.
[0294] The OLED D including the first emitting part 710 providing
the blue emission and the second emitting part 730 providing the
yellow-green emission, emits a white light.
[0295] Referring to FIG. 7, the organic emitting layer 462 includes
a first emitting part 530 including a first EML 520, a second
emitting part 550 including a second EML 540, a third emitting part
570 including a third EML 560, a first CGL 580 between the first
and second emitting parts 530 and 550 and a second CGL 590 between
the second and third emitting parts 550 and 570.
[0296] The first CGL 580 is positioned between the first and second
emitting parts 530 and 550, and the second CGL 590 is positioned
between the second and third emitting parts 550 and 570. Namely,
the first emitting part 530, the first CGL 580, the second emitting
part 550, the second CGL 590 and the third emitting part 570 are
sequentially stacked on the first electrode 460. In other words,
the first emitting part 530 is positioned between the first
electrode 460 and the first CGL 570, the second emitting part 550
is positioned between the first and second CGLs 580 and 590, and
the third emitting part 570 is positioned between the second
electrode 460 and the second CGL 590.
[0297] The first emitting part 530 may include an HIL 532, a first
HTL 534, a first EBL 536, the first EML 520 and a first HBL 538
sequentially stacked on the first electrode 460. For example, the
HIL 532, the first HTL 534 and the first EBL 536 are positioned
between the first electrode 460 and the first EML 520, and the
first HBL 538 is positioned between the first EML 520 and the first
CGL 580.
[0298] The first EML 520 includes the emitting compound in Formula
1 as a first compound 522 and provides blue emission. For example,
the first compound 522 in the first EML 520 may be one of the
compounds in Formula 6.
[0299] The EML 520 may further include a second compound 524. For
example, the second compound 524 may be represented by Formula 7
and may be one of the compounds in Formula 8.
[0300] In the first EML 520, the first compound 522 has a weight %
being smaller than the second compound 524. The first compound 522
may act as a dopant (an emitter), and the second compound 524 may
act as a host. For example, in the first EML 520, the first
compound 522 may have a weight % of about 0.1 to 30. To provide
sufficient emitting efficiency and lifespan, the weight % of the
first compound 522 may be about 0.1 to 10, or about 1 to 5.
[0301] The first EBL 536 may include the compound in Formula 9 as
the electron blocking material. In addition, the first HBL 538 may
include at least one of the compounds in Formula 11 and Formula 13
as the hole blocking material.
[0302] The second EML 550 may include a second HTL 552, the second
EML 540 and an electron transporting layer (ETL) 554. The second
HTL 552 is positioned between the first CGL 580 and the second EML
540, and the ETL 554 is positioned between the second EML 540 and
the second CGL 590.
[0303] The second EML 540 may be a yellow-green EML. For example,
the second EML 540 may include a host and a yellow-green
dopant.
[0304] Alternatively, the second EML 540 may include a host, a red
dopant and a green dopant. In this instance, the second EML 540 may
has a single-layered structure or a double-layered structure of a
lower layer including the host and the red dopant (or the green
dopant) and an upper layer including the host and the green dopant
(or the red dopant).
[0305] The second EML 540 may have a triple-layered structure of a
first layer, which includes a host and a red dopant, a second
layer, which includes a host and a yellow-green dopant, and a third
layer, which includes a host and a green dopant.
[0306] The third emitting part 570 may include a third HTL 572, a
second EBL 574, the third EML 560, a second HBL 576 and an EIL
578.
[0307] The third EML 560 includes the emitting compound in Formula
1 as a third compound 562 and provides blue emission. For example,
the third compound 562 in the third EML 560 may be one of the
compounds in Formula 6.
[0308] The third EML 560 may further include a fourth compound 564.
For example, the fourth compound 564 may be represented by Formula
7 and may be one of the compounds in Formula 8.
[0309] In the third EML 560, the third compound 562 may have a
weight % being less than the fourth compound 564. In the third EML
560, the third compound 562 may act as a dopant (an emitter), and
the fourth compound 564 may act as a host. For example, in the
third EML 560, the third compound 562 has a weight % of about 0.1
to 30. To provide sufficient emitting efficiency and lifespan, the
weight % of the third compound 562 may be about 0.1 to 10, or about
1 to 5.
[0310] The third compound 562 in the third EML 560 and the first
compound 522 in the first EML 520 may be same or different, and the
fourth compound 564 in the third EML 560 and the second compound
524 in the first EML 520 may be same or different. In addition, the
weight % of the first compound 522 in the first EML 520 and the
weight % of the third compound 562 in the third EML 560 may be same
or different.
[0311] The second EBL 574 may include the electron blocking
material in Formula 9. In addition, the second HBL 576 may include
at least one of the hole blocking material in Formula 11 and the
hole blocking material in Formula 13.
[0312] The first CGL 580 is positioned between the first emitting
part 530 and the second emitting part 550, and the second CGL 590
is positioned between the second emitting part 550 and the third
emitting part 570. Namely, the first and second emitting stacks 530
and 550 are connected through the first CGL 580, and the second and
third emitting stacks 550 and 570 are connected through the second
CGL 590. The first CGL 580 may be a P-N junction CGL of a first
N-type CGL 582 and a first P-type CGL 584, and the second CGL 590
may be a P-N junction CGL of a second N-type CGL 592 and a second
P-type CGL 594.
[0313] In the first CGL 580, the first N-type CGL 582 is positioned
between the first HBL 538 and the second HTL 552, and the first
P-type CGL 584 is positioned between the first N-type CGL 582 and
the second HTL 552.
[0314] In the second CGL 590, the second N-type CGL 592 is
positioned between the ETL 554 and the third HTL 572, and the
second P-type CGL 594 is positioned between the second N-type CGL
592 and the third HTL 572.
[0315] In the OLED D, since each of the first and third EMLs 520
and 560 includes the emitting compound in Formula 1 as the first
and third compounds 522 and 562, respectively, the emitting
efficiency and the lifespan of the OLED D and the organic light
emitting display device 400 are improved.
[0316] In addition, the OLED D including the first and third
emitting parts 530 and 570 with the second emitting part 550, which
emits yellow-green light or red/green light, can emit white
light.
[0317] In FIG. 7, the OLED D has a triple-stack structure of the
first, second and third emitting parts 530, 550 and 570.
Alternatively, the OLED D may further include additional emitting
part and CGL.
[0318] Referring to FIG. 5 again, a second electrode 464 is formed
over the substrate 410 where the organic emitting layer 462 is
formed.
[0319] In the organic light emitting display device 400, since the
light emitted from the organic emitting layer 462 is incident to
the color filter layer 480 through the second electrode 464, the
second electrode 464 has a thin profile for transmitting the
light.
[0320] The first electrode 460, the organic emitting layer 462 and
the second electrode 464 constitute the OLED D.
[0321] The color filter layer 480 is positioned over the OLED D and
includes a red color filter 482, a green color filter 484 and a
blue color filter 486 respectively corresponding to the red, green
and blue pixels RP, GP and BP. The red color filter 482 may include
at least one of red dye and red pigment, the green color filter 482
may include at least one of green dye and green pigment, and the
blue color filter 482 may include at least one of blue dye and blue
pigment.
[0322] Although not shown, the color filter layer 480 may be
attached to the OLED D by using an adhesive layer. Alternatively,
the color filter layer 480 may be formed directly on the OLED
D.
[0323] An encapsulation film (not shown) may be formed to prevent
penetration of moisture into the OLED D. For example, the
encapsulation film may include a first inorganic insulating layer,
an organic insulating layer and a second inorganic insulating layer
sequentially stacked, but it is not limited thereto. The
encapsulation film may be omitted.
[0324] A polarization plate (not shown) for reducing an ambient
light reflection may be disposed over the top-emission type OLED D.
For example, the polarization plate may be a circular polarization
plate.
[0325] In the OLED of FIG. 5, the first and second electrodes 460
and 464 are a reflection electrode and a transparent (or
semi-transparent) electrode, respectively, and the color filter
layer 480 is disposed over the OLED D. Alternatively, when the
first and second electrodes 460 and 464 are a transparent (or
semi-transparent) electrode and a reflection electrode,
respectively, the color filter layer 480 may be disposed between
the OLED D and the first substrate 410.
[0326] A color conversion layer (not shown) may be formed between
the OLED D and the color filter layer 480. The color conversion
layer may include a red color conversion layer, a green color
conversion layer and a blue color conversion layer respectively
corresponding to the red, green and blue pixels RP, GP and BP. The
white light from the OLED D is converted into the red light, the
green light and the blue light by the red, green and blue color
conversion layer, respectively. For example, the color conversion
layer may include a quantum dot. Accordingly, the color purity of
the organic light emitting display device 400 may be further
improved.
[0327] The color conversion layer may be included instead of the
color filter layer 480.
[0328] As described above, in the organic light emitting display
device 400, the OLED D in the red, green and blue pixels RP, GP and
BP emits the white light, and the white light from the organic
light emitting diode D passes through the red color filter 482, the
green color filter 484 and the blue color filter 486. As a result,
the red light, the green light and the blue light are provided from
the red pixel RP, the green pixel GP and the blue pixel BP,
respectively.
[0329] In FIGS. 5 to 7, the OLED D emitting the white light is used
for a display device. Alternatively, the OLED D may be formed on an
entire surface of a substrate without at least one of the driving
element and the color filter layer to be used for a lightening
device. The display device and the lightening device each including
the OLED D of the present disclosure may be referred to as an
organic light emitting device.
[0330] FIG. 8 is a schematic cross-sectional view illustrating an
organic light emitting display device according to a third aspect
of the present disclosure.
[0331] As shown in FIG. 8, the organic light emitting display
device 600 includes a first substrate 610, where a red pixel BP, a
green pixel GP and a blue pixel BP are defined, a second substrate
670 facing the first substrate 610, an OLED D, which is positioned
between the first and second substrates 610 and 670 and providing
white emission, and a color conversion layer 680 between the OLED D
and the second substrate 670.
[0332] Although not shown, a color filter may be formed between the
second substrate 670 and each color conversion layer 680.
[0333] Each of the first and second substrates 610 and 670 may be a
glass substrate or a flexible substrate. For example, each of the
first and second substrates 410 and 470 may be a polyimide (PI)
substrate, a polyethersulfone (PES) substrate, a
polyethylenenaphthalate (PEN) substrate, a polyethylene
terephthalate (PET) substrate or a polycarbonate (PC)
substrate.
[0334] A TFT Tr, which corresponding to each of the red, green and
blue pixels RP, GP and BP, is formed on the first substrate 610,
and a passivation layer 650, which has a drain contact hole 652
exposing an electrode, e.g., a drain electrode, of the TFT Tr is
formed to cover the TFT Tr.
[0335] The OLED D including a first electrode 660, an organic
emitting layer 662 and a second electrode 664 is formed on the
passivation layer 650. In this instance, the first electrode 660
may be connected to the drain electrode of the TFT Tr through the
drain contact hole 652.
[0336] A bank layer 666 is formed on the passivation layer 650 to
cover an edge of the first electrode 660. Namely, the bank layer
666 is positioned at a boundary of the pixel and exposes a center
of the first electrode 460 in the pixel. Since the OLED D emits the
blue light in the red, green and blue pixels RP, GP and BP, the
organic emitting layer 162 may be formed as a common layer in the
red, green and blue pixels RP, GP and BP without separation. The
bank layer 466 may be formed to prevent a current leakage at an
edge of the first electrode 460 and may be omitted.
[0337] The OLED D emits a blue light and may have a structure shown
in FIG. 3 or FIG. 4. Namely, the OLED D is formed in each of the
red, green and blue pixels RP, GP and BP and provides the blue
light.
[0338] The color conversion layer 680 includes a first color
conversion layer 682 corresponding to the red pixel RP and a second
color conversion layer 684 corresponding to the green pixel GP. For
example, the color conversion layer 680 may include an inorganic
color conversion material such as a quantum dot. The color
conversion layer 680 is not presented in the blue pixel BP such
that the OLED D in the blue pixel BP may directly face the second
substrate 670.
[0339] The blue light from the OLED D is converted into the red
light by the first color conversion layer 682 in the red pixel RP,
and the blue light from the OLED D is converted into the green
light by the second color conversion layer 684 in the green pixel
GP.
[0340] Accordingly, the organic light emitting display device 600
can display a full-color image.
[0341] On the other hand, when the light from the OLED D passes
through the first substrate 610, the color conversion layer 680 is
disposed between the OLED D and the first substrate 610.
[0342] It will be apparent to those skilled in the art that various
modifications and variations can be made in the aspects of the
present disclosure without departing from the spirit or scope of
the present disclosure. Thus, it is intended that the modifications
and variations cover this disclosure provided they come within the
scope of the appended claims and their equivalents.
* * * * *